COMPOSITION, ITS POLYMERIZATION PROCESS, ITS USE, AN OBJECT OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION AND RECYCLING

Abstract

The present invention relates to a composition for the preparation of polymers comprising a precursor or prepolymer for thermosetting polymers. In particular, the present invention relates to a recyclable composition comprising a thermosetting polymer, its polymerization process and a resulting object, as well as a recycling process. The present invention also relates to a process for manufacturing thermoplastic composites, mechanical parts or structural elements composed of composite material, and mechanical parts or structural elements composed of composite material obtained via the process using such a composition comprising a precursor or prepolymer for thermosetting polymers, and a recycling process.

Description

Title of the invention: COMPOSITION, its POLYMERIZATION PROCESS, ITS use, AN OBJECT OBTAINED AFTER POLYMERIZATION of the composition and RECYCLING technical field

[0001] The present invention relates to a composition for the preparation of polymers comprising a precursor or a prepolymer for thermosetting polymers.

[0002] In particular, the present invention relates to a recyclable composition comprising a thermosetting polymer, its polymerization process and an object obtained, as well as a recycling process.

[0003] The present invention also relates to a method for manufacturing thermoplastic composites, mechanical parts or structural elements composed of composite material and mechanical parts or structural elements composed of composite material obtained via the process using such a composition comprising a precursor or prepolymer for thermosetting polymers and a method for recycling. Previous technique

[0004] Thermosetting polymers are materials that are widely used today in several fields and applications, for example in the construction, aeronautical, automotive or railway sectors, where they are part of mechanical parts.

[0005] These mechanical parts, which must withstand high stresses during their use, are largely manufactured from composite materials. A composite material is a macroscopic combination of two or more immiscible materials. The composite material consists of at least one material that forms the matrix, that is, a continuous phase that ensures the cohesion of the structure, and a reinforcing material.

[0006] The objective of using a composite material is to obtain performance qualities that cannot be obtained from each of its constituents when used separately. Consequently, composite materials are widely used in several industrial sectors, for example construction, automotive, aerospace, transportation, leisure, electronics, and sports, particularly because of their superior mechanical performance (higher tensile strength, higher tensile modulus, higher fracture toughness) and their low density, compared to homogeneous materials.

[0007] However, recycling thermosetting materials can be very difficult, inefficient, or even sometimes almost impossible. Often, the product is ground into small powders, which are used as fillers, or not recycled at all, such as epoxy resin-based composite wind turbine blades that are stored in landfills, or thermosetting composites that are incinerated.

[0008] Thermoset polymers are highly cross-linked during the curing stage; they cannot be remelted or reprocessed. Consequently, they cannot be recycled as thermoplastic polymers, which can either be depolymerized to recover the respective monomers, or reprocessed, for example, by granulating the article or object to be recycled into a thermoplastic polymer followed by reinjection or reextrusion.

[0009] Chemical recycling is not easy and requires very specific monomers or crosslinking agents in the thermosetting polymer for hydrolysis or decrosslinking. Or, in the case of thermosetting polymer composites, if the interest lies solely in the fibrous part, chemical recycling requires specific (harmful) solvents.

[0010] In the case of recycling thermoset polymer composites where only the fibrous part is recovered, recycling can also be thermal by pyrolysis or fluidized bed technologies.

[0011] Document WO2023 / 174747 discloses ground composite materials used in curable epoxy compositions. The composite material comprises either an unsaturated polyester resin or a cured epoxy resin. The ground material has a particle size distribution well below 1 mm, or even below 500 µm.

[0012] Document WO2018 / 006090 describes methods for remodeling and recycling thermoset polymers and composites containing thermoset polymers. The methods involve the bond exchange reaction of exchangeable covalent bonds in the polymer matrix with a suitable small-molecule solvent in the presence of a catalyst.

[0013] Document WO2022 / 238128 discloses a reactive diluent composition based on (meth)acrylate for unsaturated polyester resins. The document substitutes styrene unsaturated polyester resins with a (meth)acrylic acid ester monomer. However, the composition does not comprise (meth)acrylic polymer.

[0014] Document WO2013 / 124273 discloses a thermosetting resin composition comprising an unsaturated polyester resin, ethylenically unsaturated compounds, benzyl methacrylate, and a resin containing a methacrylate, the latter being a reaction product of an oligomer or polymer epoxy with methacrylic acid or methacrylamide. The polymer matrix does not include (meth)acrylic polymer.

[0015] It is not disclosed or suggested in any of these documents that a composition comprising the four components (a1) a (meth)acrylic polymer (PI), (a2) a (meth)acrylic monomer (M1), an unsaturated polyester (UP1) or a vinyl ester resin (VE1) and a monomer (M2) in the respective ranges, gives a composition comprising a recyclable thermoset polymer or a composite or article comprising a recyclable thermoset polymer. [TECHNICAL PROBLEM]

[0016] The objective of the invention is, therefore, to remedy at least one of the drawbacks of the prior art.

[0017] An objective of the present invention is to have a composition comprising a precursor of a thermosetting polymer which, once the composition has polymerized, can be recycled or more easily recycled, including the polymeric part.

[0018] The present invention also aims to provide a method for recycling a polymer composition or a polymeric article or a polymeric composite, comprising a thermoset polymer.

[0019] Another objective of the present invention is to use a composition comprising a prepolymer or precursor of a thermosetting polymer to produce a more easily recyclable polymer composition or a polymeric article or a polymeric composite comprising a thermosetting polymer.

[0020] Yet another objective of the present invention is to provide a composition for the preparation of compositions comprising a thermosetting polymer or of composites comprising a thermosetting polymer and a method for recycling such compositions comprising a thermosetting polymer or of composites comprising a thermosetting polymer.

[0021] Yet another objective of the present invention is to propose a composition for the preparation of compositions comprising a thermoset polymer or of composites comprising a thermoset polymer for a faster process of recycling such compositions comprising a thermoset polymer or of composites comprising a thermoset polymer. [BRIEF DESCRIPTION OF THE INVENTION]

[0022] It has been discovered that a liquid composition (LC1) comprising:

[0023] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0024] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0025] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0026] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0027] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0028] (b2) from 20% by weight to 60% by weight of one or more monomers (M2),

[0029] (c) possibly from 0.01 parts by weight to 7 parts by weight of an initiator of polymerization (INI1),

[0030] (d) possibly between 100 ppm and 20,000 ppm from an accelerator,

[0031] makes it possible to provide a composition comprising a precursor of a thermoset polymer, which, once the composition is polymerized, can be recycled or more easily recycled compared to a composition not comprising the (meth)acrylic composition (MCI).

[0032] It was also discovered that a liquid composition (LC1) comprising:

[0033] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0034] (ai) of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0035] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0036] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0037] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0038] (b2) from 20% by weight to 60% by weight of one or more monomers (M2),

[0039] (c) from 0.01 parts by weight to 7 parts by weight of a polymerization initiator (INI1),

[0040] (d) between 100 ppm and 20,000 ppm of an accelerator, and

[0041] (e) possibly a thixotropic agent,

[0042] makes it possible to provide a composition comprising a precursor of a thermosetting polymer, which, once the composition is polymerized, can be recycled or more easily recycled compared to a composition not including the (meth)acrylic (MCI) composition.

[0043] It has also been discovered that the process for manufacturing composites, preferably thermoset polymers comprising composites (TPCO), said process comprising the following steps:

[0044] i) impregnation of fibers or fibrous material with a liquid composition (LC1) comprising:

[0045] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0046] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0047] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0048] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0049] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0050] (b2) from 20% by weight to 60% by weight of one or more monomers (M2),

[0051] (c) possibly from 0.01 parts by weight to 7 parts by weight of an initiator of polymerization (INI1),

[0052] (d) possibly between 100 ppm and 20,000 ppm of an accelerator

[0053] ii) polymerization of the liquid composition (LC1) that has impregnated the fibrous material,

[0054] gives a composite comprising a thermoset polymer, which can be recycled or more easily recycled compared with a composite not comprising the (meth)acrylic (MCI) composition.

[0055] A process (100) for recycling a composite comprising a thermoset polymer, based on a polymerized liquid composition (LC1), has also been discovered, said process comprising the following steps:

[0056] - possibly a cutting step,

[0057] - a step of grinding the composition comprising a thermosetting polymer or of the composite comprising a thermosetting polymer;

[0058] leads to an easy recycling process. Description of the implementation methods

[0059] According to a first aspect, the present invention relates to a liquid composition (LC1) comprising:

[0060] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0061] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0062] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0063] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0064] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0065] (b2) from 20% by weight to 60% by weight of one or more monomers (M2),

[0066] (c) possibly from 0.01 parts by weight to 7 parts by weight of an initiator of polymerization (INI1),

[0067] (d) possibly between 100 ppm and 20,000 ppm from an accelerator.

[0068] According to a second aspect, the present invention relates to a liquid composition (LC1) comprising:

[0069] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0070] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0071] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0072] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0073] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0074] (b2) from 20% by weight to 60% by weight of one or more monomers (M2),

[0075] (c) from 0.01 parts by weight to 7 parts by weight of a polymerization initiator (INI1),

[0076] (d) between 100 ppm and 20,000 ppm of an accelerator.

[0077] According to a third aspect, the present invention relates to the use of a liquid composition (LC1) comprising:

[0078] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0079] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0080] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0081] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0082] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0083] (b2) from 20% by weight to 60% by weight of one or more monomers (M2),

[0084] (c) possibly from 0.01 parts by weight to 7 parts by weight of an initiator of polymerization (INI1),

[0085] (d) possibly between 100 ppm and 20,000 ppm from an accelerator,

[0086] for the preparation of a recyclable polymer composition or a recyclable polymeric article or a recyclable composite composition or a recyclable polymeric composite all comprising a thermoset polymer.

[0087] According to a fourth aspect, the present invention relates to the use of a liquid composition (LC1) comprising:

[0088] (a) 100 parts by weight of a liquid (meth)acrylic composition MCI including:

[0089] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0090] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0091] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0092] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0093] (b2) from 20% by weight to 60% by weight of one or more monomers M2, each monomer M2 comprising only one polymerizable function per monomer

[0094] (c) from 0.01 parts by weight to 7 parts by weight of a polymerization initiator (INI1),

[0095] (d) between 100 ppm and 20,000 ppm of an accelerator,

[0096] for the preparation of a recyclable polymer composition or a recyclable polymeric article or a recyclable polymeric composite comprising a thermoset polymer

[0097]

[0098] According to a fifth aspect, the present invention relates to a method for manufacturing composites by a process comprising the following steps:

[0099] i) impregnation of fibres or fibrous material with the liquid composition (LC1) according to the first or second aspect,

[0100] ii) polymerization of the liquid composition (LC1).

[0101] According to a sixth aspect, the present invention relates to a process (100) for recycling a thermoset polymer comprising a composition (TPC) or a composite comprising a thermoset polymer (TPCO) obtained by polymerization of the liquid composition (LC1) according to the first or second aspect, said process comprising the following steps:

[0102] - possibly a cutting step,

[0103] - a step of grinding the composition comprising a thermosetting polymer or of the composite comprising a thermoset polymer.

[0104] The term “fibrous substrate”, in this context, means several fibers, unidirectional strands or continuous filament mat, fabrics, felts or nonwovens which may be in the form of strips, sheets, braids, strands or pieces.

[0105] The term “(meth)acrylic”, in the present context, refers to any type of acrylic or methacrylic monomer.

[0106] The term “PMMA”, in the present context, refers to homopolymers and copolymers of methyl methacrylate (MMA), the weight ratio of MMA in PMMA being at least 70% by weight for the MMA copolymer.

[0107] The term “monomer”, in the present context, refers to a molecule that can undergo polymerization.

[0108] The term “polymerization”, in this context, refers to the process of converting a monomer or a mixture of monomers into a polymer.

[0109] The term “thermoplastic polymer,” in this context, refers to a polymer that becomes liquid or more liquid or less viscous or soft when heated and that can take on new shapes through the application of heat and pressure. This also applies to thermoplastic polymers. slightly cross-linked which can be thermoformed when heated above the softening temperature.

[0110] The term "thermosetting polymer" means a polymer obtained by hardening (extensive crosslinking) a soft solid or viscous liquid prepolymer. The thermosetting polymer alone cannot be melted for reshaping.

[0111] The terms “polymer composite”, in this context, refer to a multicomponent material comprising several different phase domains, among which at least one type of phase domain is a continuous phase and in which at least one component is a polymer.

[0112] The term “initiator”, in the present context, refers to a compound that can start / initiate the polymerization of a monomer or monomers.

[0113] The abbreviation "phr" denotes parts by weight per hundred parts of composition. For example, 1 phr of initiator in the composition means that 1 kg of initiator is added to 100 kg of composition.

[0114] The abbreviation "ppm" stands for parts by weight per million parts of composition. For example, 1000 ppm of a compound in the composition means that 0.1 kg of the compound is present in 100 kg of the composition.

[0115] By specifying that a range goes from x to y in the present invention, this means that the upper and lower limits of this range are included, which is equivalent to at least x and up to y.

[0116] By specifying that a range is between x and y in the present invention, this means that the upper and lower limits of this range are excluded, which is equivalent to more than x and less than y.

[0117] The liquid composition (LC1) according to the invention comprises at least one liquid (meth)acrylic composition (MCI) and one composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC).

[0118] According to a first preferred embodiment, the liquid composition (LC1) further comprises a polymerization initiator (INI1).

[0119] According to a second preferred embodiment, the liquid composition (LC1) further comprises an accelerator.

[0120] According to a third preferred embodiment, the liquid composition (LC1) comprises a thixotropic agent.

[0121] Preferably, the viscosity or dynamic viscosity of the liquid composition (LC1) is in the range of 10 mPa*s to 10,000 mPa*s, preferably from 20 mPa*s to 9,000 mPa*s, and advantageously from 30 mPa*s to 8,000 mPa*s and more advantageously from 40 mPa*s to 7,500 mPa*s and even more advantageously between 50 mPa*s and 7,000 mPa*s. The viscosity of the liquid composition (LC1) may It can be easily measured using a rheometer or viscometer. Dynamic viscosity is measured at 25 °C. If the liquid (meth)acrylic syrup exhibits Newtonian behavior, meaning it does not thin under shear, the dynamic viscosity is independent of shear rate in a rheometer or of the moving part's velocity in a viscometer. If the liquid composition exhibits non-Newtonian behavior, meaning it thins under shear, the dynamic viscosity is measured at a shear rate of 1 s⁻¹ at 25 °C.

[0122] The liquid composition (LC1) according to the invention, includes in particular at least one liquid (meth)acrylic composition (MCI) and a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC).

[0123] The liquid composition (LC1) according to the invention comprises at least:

[0124] a) 100 parts by weight of a liquid (meth)acrylic (MCI) composition comprising:

[0125] (aO of 10% by weight to 50% by weight of one or more (meth) acrylic polymers (PI), and

[0126] (a2) from 50% by weight to 90% by weight of one or more monomers (meth)acrylics (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer.

[0127] (b) from 50 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester (UPC) composition, or a vinyl ester (VEC) composition comprising:

[0128] (bi) of 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and

[0129] (b2) from 20% by weight to 60% by weight of one or more monomers (M2).

[0130] As regards the liquid composition (LC1) of the invention, it comprises, among other components, a (meth)acrylic monomer (M1) and one or more monomers (M2). Preferably, the monomer (M2) is different from the monomer (M1).

[0131] The amount of polymerization initiator (Inil) in the liquid composition (LC1) is at least 0.01 phr relative to the sum of a liquid (meth)acrylic composition (MCI) and a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC). Preferably, the amount of polymerization initiator (Inil) in the composition is at least 0.1 phr, more preferably at least 0.2 phr, even more preferably at least 0.3 phr, and advantageously at least 0.5 phr relative to the sum of a liquid (meth)acrylic composition (MCI) and composition (C2).

[0132] The amount of polymerization initiator (Inil) in composition (LC1) is at most 7 phr relative to the sum of a liquid (meth)acrylic composition (MCI) and a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC). Preferably, the amount of polymerization initiator (Inil) in composition (LC1) is at most 6.5 phr, more preferably at most 6 phr, even more preferably at most 5.5 phr, and advantageously at most 5 phr relative to the sum of a liquid (meth)acrylic composition (MCI) and a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC).

[0133] The amount of polymerization initiator (Inil) in the composition is between 0.01 phr and 7 phr relative to the sum of a liquid (meth)acrylic composition (MCI) and a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC). Preferably, the amount of at least one initiator (Inil) in the composition is between 0.1 phr and 6.5 phr, more preferably between 0.2 phr and 6 phr, even more preferably between 0.3 phr and 5.5 phr, and advantageously between 0.5 phr and 5 phr relative to the sum of a liquid (meth)acrylic composition (MCI) and a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC).

[0134] With regard to the (meth)acrylic (Ml) monomer of the liquid (meth)acrylic composition (MCI), the monomer is chosen from acrylic acid, methacrylic acid, alkylacrylic monomers, alkylmethacrylic monomers, hydroxyalkylacrylic monomers and hydroxyalkylmethacrylic monomers and mixtures thereof.

[0135] Preferably, the (meth)acrylic monomer (Ml) is selected from acrylic acid, methacrylic acid, hydroxyalkyl acrylic monomers, hydroxyalkyl methacrylic monomers, alkyl acrylic monomers, alkyl methacrylic monomers and mixtures thereof, the alkyl group containing from 1 to 22 linear, branched or cyclic carbons; the alkyl group preferably containing from 1 to 12 linear, branched or cyclic carbons.

[0136] Advantageously, the (meth)acrylic monomer (Ml) is selected from methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate and mixtures thereof.

[0137] According to a preferred embodiment, at least 50% by weight and preferably at least 60% by weight of the (meth)acrylic monomer (Ml) is methyl methacrylate.

[0138] According to a first more preferred embodiment, at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight, advantageously at least 80% by weight and even more advantageously 90% by weight of the monomer (Ml) is a mixture of methyl methacrylate with optionally at least one other monomer.

[0139] With regard to the (meth)acrylic (PI) polymer of the liquid (meth)acrylic composition (MCI), mention may be made of poly(alkyl methacrylate) or poly(alkyl acrylate). According to a preferred embodiment, the (meth)acrylic polymer is poly(methyl methacrylate) (PMMA).

[0140] The term “PMMA” refers to a homopolymer or copolymer of methyl methacrylate (MMA) or mixtures thereof.

[0141] According to one embodiment, the methyl methacrylate (MMA) homopolymer or copolymer comprises at least 70%, preferably at least 80%, advantageously at least 90% and more advantageously at least 95% by weight of methyl methacrylate.

[0142] According to another embodiment, PMMA is a mixture of at least one homopolymer and at least one copolymer of MMA, or a mixture of at least two homopolymers or two copolymers of MMA having a different average molecular weight, or a mixture of at least two copolymers of MMA having a different monomer composition.

[0143] The methyl methacrylate (MMA) copolymer comprises from 70% to 99.7% by weight of methyl methacrylate and from 0.3% to 30% by weight of at least one monomer containing at least one ethylenic unsaturation which can copolymerize with methyl methacrylate.

[0144] These monomers are well known, and in particular include acrylic and methacrylic acids and alkyl (meth)acrylates in which the alkyl group contains from 1 to 12 carbon atoms. Examples include methyl acrylate and ethyl, butyl, or 2-ethylhexyl (meth)acrylate. Preferably, the comonomer is an alkyl acrylate in which the alkyl group contains from 1 to 4 carbon atoms.

[0145] According to a first preferred embodiment, the methyl methacrylate (MMA) copolymer comprises 80% to 99%, advantageously 90% to 99.7% and more advantageously 90% to 99.5% by weight of methyl methacrylate and 0.3% to 20%, advantageously 0.3% to 10% and more advantageously 0.5% to 10% by weight of at least one monomer containing at least one ethylenic unsaturation which It can copolymerize with methyl methacrylate. Preferably, the comonomer is chosen from methyl acrylate and ethyl acrylate and mixtures thereof.

[0146] The average molecular mass by weight of the (meth)acrylic (PI) polymer should be relatively high, meaning greater than 50,000 g / mol and preferably greater than 70,000 g / mol.

[0147] The average molecular mass by weight can be measured by size exclusion chromatography (SEC).

[0148] The (meth)acrylic polymer is completely soluble in the (meth)acrylic monomer or in the mixture of (meth)acrylic monomers. This increases the viscosity of the (meth)acrylic monomer or the mixture of (meth)acrylic monomers. The resulting solution is a liquid composition generally referred to as a "syrup" or "prepolymer." The dynamic viscosity of the liquid (meth)acrylic syrup ranges from 10 mPa·s to 10,000 mPa·s. The viscosity of the syrup can be easily measured using a rheometer or viscometer. The dynamic viscosity is measured at 25 °C.

[0149] Advantageously, the liquid (meth)acrylic composition (MCI) does not contain any additional solvents intentionally added.

[0150] Composition (C2) comprises either an unsaturated polyester composition (UPC), a vinyl ester composition (VEC), or a mixture.

[0151] According to a first preferred embodiment, the composition (C2) comprises an unsaturated polyester (UPC) composition.

[0152] According to a second preferred embodiment, the composition (C2) comprises a vinyl ester composition (VEC).

[0153] According to a third preferred embodiment, the composition (C2) comprises a mixture of an unsaturated polyester composition (UPC) and a vinyl ester composition (VEC).

[0154] According to a fourth preferred embodiment, the composition (C2) is an unsaturated polyester (UPC) composition.

[0155] According to a fifth preferred embodiment, the composition (C2) is a vinyl ester (VEC) composition.

[0156] With regard to the unsaturated polyester (UPC) composition of composition (C2), it is the precursor of a thermoset polymer.

[0157] The unsaturated polyester composition (UPC) comprises from 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) and from 20% by weight to 60% by weight of one or more monomers (M2), each monomer (M2) comprising only one polymerizable function per monomer.

[0158] In a first preferred embodiment, the unsaturated polyester (UPC) composition comprises from 45% by weight to 80% by weight of one or more polyesters unsaturated (UP1) and 20% by weight to 55% by weight of one or more monomers (M2).

[0159] In a second preferred embodiment, the unsaturated polyester composition (UPC) comprises from 40% by weight to 70% by weight of one or more unsaturated polyesters (UP1) and from 30% by weight to 60% by weight of one or more monomers (M2).

[0160] In a third preferred embodiment, the unsaturated polyester composition (UPC) comprises from 40% by weight to 60% by weight of one or more unsaturated polyesters (UP1) and from 40% by weight to 60% by weight of one or more monomers (M2).

[0161] The unsaturated polyester(s) (UP1) are selected from a condensation product of polyols with unsaturated and, in some cases, saturated dibasic acids or anhydrides. The polyols may be glycols such as neopentyl glycol, ethylene glycol, 1,2-propylene glycol, and diethylene glycol; but also glycerol, trimethylolpropane, or trimethylolpropane monoallyl ether. The unsaturated dibasic acids or anhydrides may be maleic anhydride, fumaric acid, or itaconic acid. The saturated dibasic acids or anhydrides may be phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, or sebacic acid.

[0162] Preferably, the monomer (M2) is different from the monomer (M1). The monomer (M2) may comprise a single polymerizable group per monomer, but also two polymerizable groups.

[0163] In a first preferred embodiment, the monomer (M2) with the unsaturated polyesters (UP1) is a vinyl monomer.

[0164] In a second preferred embodiment, the monomer (M2) with the unsaturated polyesters (UP1) is a monomer containing a vinyl aromatic compound.

[0165] In a third preferred embodiment, the monomer (M2) with the unsaturated polyesters (UP1) is styrene.

[0166] In a fourth preferred embodiment, the monomer (M2) with the unsaturated polyesters (UP1) is an acrylic or methacrylic monomer or a diacrylic or dimethacrylic monomer.

[0167] In a fourth preferred embodiment, the monomer (M2) with the unsaturated polyesters (UP1) is an allylic monomer or a diallylic monomer.

[0168] As regards the vinyl ester (VEC) composition of composition (C2), it is the precursor of a thermoset polymer.

[0169] The vinyl ester composition (VEC) comprises from 40% by weight to 80% by weight of a vinyl ester resin (VE1) and from 20% by weight to 60% by weight of one or more monomers (M2).

[0170] In a first preferred embodiment, the vinyl ester composition (VEC) comprises from 45% by weight to 80% by weight of a vinyl ester resin (VE1) and from 55% by weight to 20% by weight of one or more monomers (M2).

[0171] In a second preferred embodiment, the vinyl ester composition (VEC) comprises from 40% by weight to 70% by weight of a vinyl ester resin (VE1) and from 60% by weight to 30% by weight of one or more monomers (M2).

[0172] In a third preferred embodiment, the vinyl ester composition (VEC) comprises from 40 wt% to 60 wt% of a vinyl ester resin (VE1) and from 60 wt% to 40 wt% of one or more monomers (M2).

[0173] The vinyl ester resin (VE1) can be selected from an addition product of an epoxide with an ethylenically unsaturated monocarboxylic acid. For example, by the reaction of a bisphenol-A glycidyl ether with methacrylic acid.

[0174] The epoxides could also be a novolac epoxy or a cycloaliphatic epoxy or diepoxidized hydrogenated bisphenol A. The unsaturated acid could also be acrylic acid, crotonic acid or cinnamic acid.

[0175] Preferably, the monomer (M2) is different from the monomer (Ml).

[0176] In a first preferred embodiment, the monomer (M2) with the vinyl ester resin (VE1) is a vinyl monomer.

[0177] In a second preferred embodiment, the monomer (M2) with the vinyl ester resin (VE1) is a styrene-containing monomer.

[0178] In a third preferred embodiment, the monomer (M2) with the vinyl ester resin (VE1) is styrene.

[0179] In a fourth preferred embodiment, the monomer (M2) with the vinyl ester resin (VE1) is an acrylic or methacrylic monomer or a diacrylic or dimethacrylic monomer.

[0180] With regard to polymerization initiators (Inil), the initiators generate radicals which initiate the monomer(s) to start a radical polymerization of the monomer in order to form the polymer chains by propagation.

[0181] In a first preferred embodiment, the initiator (Inil) is activated by heat.

[0182] In a second preferred embodiment, the initiator (Inil) is activated by an activator or an accelerator.

[0183] The initiator to be activated (Inil) is preferably a radical initiator.

[0184] The radical initiator (Inil) can be chosen from a compound comprising a peroxy group or compounds comprising an azo group and, preferably, from a compound comprising a peroxy group.

[0185] Preferably, the compound comprising a peroxy group comprises from 2 to 50 carbon atoms.

[0186] Preferably, the compound comprising a peroxy group is selected from diacyl peroxides, peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyacetals, a hydroperoxide, a ketone peroxide or a peroxyketal.

[0187] The initiator (Inil) can have a half-life ti / 2 of 1 hour at a temperature between 40 °C and 150 °C.

[0188] In a first preferred embodiment, the initiator (Inil) is chosen from a peroxydicarbonate.

[0189] In a second preferred embodiment, the initiator (Inil) is chosen from a ketone peroxide.

[0190] In a third preferred embodiment, the initiator (Inil) is chosen from a diacyl peroxide.

[0191] In a fourth preferred embodiment, the initiator (Inil) is chosen from a peroxycetal.

[0192] In a fifth preferred embodiment, the initiator (Inil) is chosen from a hydroperoxide.

[0193] Preferably, the initiator (Inil) has a maximum storage temperature of 25 °C or less.

[0194] In order to maintain a dynamic viscosity of the liquid composition (LC1), which also allows good impregnation of the fibrous substrate if necessary, and to maintain the properties of the matrix obtained after polymerization of the fibrous substrate impregnated with the liquid composition (LC1), the components of the composition are incorporated in the following mass percentages:

[0195] of 50 parts by weight to 150 parts by weight of the composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

[0196] In a first preferred embodiment, the liquid composition (LC1) comprises from 50 parts by weight to 100 parts by weight of a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

[0197] In a second preferred embodiment, the liquid composition (LC1) comprises from 50 parts by weight to 80 parts by weight of a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

[0198] In a third preferred embodiment, the liquid composition (LC1) comprises from 80 parts by weight to 150 parts by weight of a composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

[0199] Preferably, the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 4% by weight relative to a composition comprising the four components (a2) (meth)acrylic monomers (Ml), (ai) (meth)acrylic polymers (PI), (bi) unsaturated polyester (UP1) or a vinyl ester resin (VE1) and (b2) monomer (M2).

[0200] More preferably, the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 5% by weight relative to a composition comprising the four components (a2) (meth)acrylic monomers (M1), (a0) (meth)acrylic polymers (PI), (bi)unsaturated polyester (UP1) or vinyl ester resin (VE1) and (b2) monomer (M2).

[0201] In a first, even more preferable embodiment, the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 7% by weight relative to a composition comprising the four components (a2) (meth)acrylic monomers (M1), (ai) (meth)acrylic polymers (PI), (bi) unsaturated polyester (UP1) or a vinyl ester resin (VE1) and (b2) monomer (M2).

[0202] In a second, even more preferable embodiment, the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 10% by weight relative to a composition comprising the four components (a2) (meth)acrylic monomers (M1), (ai) (meth)acrylic polymers (PI), (bi) unsaturated polyester (UP1) or a vinyl ester resin (VE1) and (b2) monomer (M2).

[0203] In a third, even more preferable embodiment, the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 12% by weight relative to a composition comprising the four components: (a2) (meth)acrylic monomers (M1), (a1) (meth)acrylic polymers (PI), (bi)unsaturated polyester (UP1) or vinyl ester resin (VE1) and (b2) monomer (M2).

[0204] In a fourth, even more preferable embodiment, the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 15% by weight relative to a composition comprising the four components (a2) (meth)acrylic monomers (M1), (aj) (meth)acrylic polymers (PI), (bi)unsaturated polyesters (UP1) or a vinyl ester resin (VE1) and (b2) monomer (M2).

[0205] The amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) can be adapted either by modifying the ratio of (meth)acrylic polymers (PI) in the liquid (meth)acrylic composition (MCI), either by modifying the ratio of the composition (C2) in the liquid composition (LC1) for a given liquid (meth)acrylic composition (MCI).

[0206] The (meth)acrylic monomer(s) (Ml) in the liquid (meth)acrylic composition (MCI) are present in proportions of between 40% and 95% by weight, preferably between 40% and 90% by weight and advantageously between 45% and 85% by weight of the composition comprising one or more (meth)acrylic monomers (Ml) and the (meth)acrylic polymer (PI).

[0207] The (meth)acrylic (PI) polymer(s) in the liquid (meth)acrylic (MCI) composition are present in a proportion of at least 5% by weight, preferably at least 10% and advantageously at least 15% by weight of the composition comprising one or more (meth)acrylic (Ml) monomer(s) and the (meth)acrylic (PI) polymer.

[0208] The (meth)acrylic (PI) polymer(s) in the liquid (meth)acrylic composition (MCI) are present in a proportion of not more than 50% by weight, preferably not more than 40% and advantageously not more than 30% by weight of the composition comprising one or more (meth)acrylic (Ml) monomers and the (meth)acrylic (PI) polymer.

[0209] All possible additives and fillers are added to the liquid (meth)acrylic (MCI) composition before impregnation and / or polymerization.

[0210] The liquid composition (LC1) according to the invention may optionally also include an activator or accelerator for polymerization.

[0211] The polymerization activator or accelerator can be chosen from tertiary amines such as N,N-dimethyl-p-toluidine (DMPT), N,N-dihydroxyethyl-p-toluidine (DHEPT), ethoxylated p-toluidine (EPT); but also diethylaniline (DEA) or dimethylaniline (DMA), organic-soluble transition metal catalysts or mixtures thereof.

[0212] The content or quantity of the activator relative to the (meth)acrylic monomer (Ml) and the monomer (M2) of the liquid composition (LC1) is from 100 ppm to 20,000 ppm (by weight), preferably from 200 ppm to 10,000 ppm by weight and advantageously from 300 ppm to 7,000 ppm.

[0213] The liquid composition (LC1) according to the invention may optionally also include a thixotropic agent.

[0214] The thixotropic agent can be chosen from fumed silica, pyrogenic silica, glass microspheres, but also polyamides, polyurethanes and modified urea.

[0215] The content or quantity of the thixotropic agent is from 0.1 phr to 10 phr in the liquid composition (LC1).

[0216] With regard to the process of manufacturing the liquid (meth)acrylic composition (MCI), a first step consists of preparing a first syrup comprising the (meth)acrylic monomer (Ml) or a mixture of (meth)acrylic monomers and a (meth)acrylic polymer (PI).

[0217] Preferably, the (meth)acrylic polymer (PI) is added to the (meth)acrylic monomers and solubilized.

[0218] With regard to the process of manufacturing the liquid composition (LC1), a first step consists of mixing the liquid (meth)acrylic composition (MCI) and the composition (C2) in the respective ratios.

[0219] Optional components are added later.

[0220] The initiator (Inil) is added at the end.

[0221] Preferably, the initiator (Inil) is added at a temperature Tadd below 50 °C, more preferably below 40 °C, advantageously below 30 °C and more advantageously below 25 °C.

[0222] According to another additional aspect, the invention relates to a method for preparing the liquid composition (LC1) comprising the following steps:

[0223] (i) supply of component (a), a liquid (meth)acrylic syrup comprising

[0224] (ai) of 1% by weight to 50% by weight of one or more PI (meth)acrylic polymers, and

[0225] (a2) from 50% by weight to 99% by weight of one or more monomers (meth)acrylic Ml, each monomer Ml comprising only one (meth)acrylic function per monomer,

[0226] (ii) adding, for 100 parts of (a), 50 to 150 parts by weight of component (b),

[0227] optionally of component (c) from 0.01 parts by weight to 7 parts by weight of a polymerization initiator (INI1) and optionally of component (d) between 100 ppm and 20,000 ppm of an accelerator

[0228] (iii) mixing components (a) with (b) or (a) with (d).

[0229] The liquid composition (LC1) according to the invention, as detailed in the preceding paragraphs, can be used for the impregnation of fibers or a fibrous substrate or for the manufacture of composite parts or a composite material (CM1), in particular for the preparation of composites by resin transfer molding (RTM), pultrusion, infusion, spray layering or manual layering.

[0230] In a first preferred embodiment, the use for impregnating fibers or a fibrous substrate is a spray-applied layering.

[0231] In a second preferred embodiment, the use for impregnating fibers or a fibrous substrate is resin transfer molding.

[0232] In a third preferred embodiment, the use for impregnating fibers or a fibrous substrate is manual layering.

[0233] With regard to the fibers or fibrous substrate, one can mention several fibers, unidirectional strands or a mat of continuous filaments, fabrics, felts or nonwovens which may be in the form of strips, sheets, braids, strands or pieces. The fibrous material may have different shapes and dimensions, namely one-dimensional, two-dimensional or three-dimensional. A fibrous substrate comprises an assembly of one or more fibers. When the fibers are continuous, their assembly forms fabrics.

[0234] The one-dimensional form corresponds to long linear fibers. The fibers may be discontinuous or continuous. The fibers may be arranged randomly or parallel to each other, in the form of a continuous filament. A fiber is defined by its aspect ratio, which is the ratio between the length and the diameter of the fiber. The fibers used in the present invention are long fibers or continuous fibers. The fibers have an aspect ratio of at least 1000, preferably at least 1500, more preferably at least 2000, advantageously at least 3000, and more advantageously at least 5000, even more advantageously at least 6000, even more advantageously at least 7500, and most preferably at least 10,000.

[0235] The two-dimensional form corresponds to fibrous mats or reinforcements or bundles of non-woven or woven fibers, which may also be braided. Even if the two-dimensional form has a certain thickness and, consequently, in principle a third dimension, it is considered to be two-dimensional according to the present invention.

[0236] The origins of the fibrous material can be natural or synthetic. As natural materials, we can mention plant fibers, wood fibers, animal fibers or mineral fibers.

[0237] Natural fibers include, for example, sisal, jute, hemp, flax, cotton, coconut fibers and banana fibers. Animal fibers include, for example, wool or hair.

[0238] As a synthetic material, mention may be made of polymer fibres selected from thermosetting polymer fibres, thermoplastic polymers or mixtures thereof.

[0239] Polymer fibres may be made of polyamide (aliphatic or aromatic), polyester, polyvinyl alcohol, polyolefins, polyurethanes, polyvinyl chloride, polyethylene, unsaturated polyesters, epoxy resins and vinyl esters.

[0240] Mineral fibres can also be selected from glass fibres, in particular of type E, R or S2, carbon fibres, boron fibres, basalt fibres or silica fibres.

[0241] The fibrous substrate of the present invention is selected from plant fibers, wood fibers, animal fibers, mineral fibers, synthetic polymer fibers, glass fibers and carbon fibers, and mixtures thereof.

[0242] Preferably, the fibrous substrate is chosen from mineral fibers.

[0243] The fibers of the fibrous substrate have a diameter between 0.005 pm and 100 pm, preferably between 1 pm and 50 pm, more preferably between 5 pm and 30 pm and advantageously between 10 pm and 25 pm.

[0244] Preferably, the fibers of the fibrous substrate of the present invention are chosen from continuous fibers (meaning that the aspect ratio does not necessarily apply as for long fibers) for the one-dimensional shape, or from long or continuous fibers for the two- or three-dimensional shape of the fibrous substrate.

[0245] The liquid composition (LC1) is used to prepare a recyclable polymeric composition (PCI) or a polymeric article or composite material (CM1) or a polymeric composite material, all comprising a thermosetting polymer. In another further aspect, the invention relates to a polymeric composition (PCI) prepared by polymerizing the liquid composition (LC1). In another further aspect, the invention relates to a thermosetting polymer comprising a composite (TPCO) comprising the polymerized liquid composition (LC1). In yet another further aspect, the invention relates to an article, object, molded part, or mechanical part made of a composite material comprising the polymeric composition (PCI) prepared by polymerizing the liquid composition (LC1).

[0246] The term recyclable applies to all these uses.

[0247] According to another additional aspect, the invention relates to a polymeric composite material (CM1), a polymeric composite material comprising a polymeric matrix and a filler fibrous substrate used as reinforcement, in which the fibrous substrate consists of long fibers, said composite material (CM1) being characterized in that the polymeric matrix is ​​obtained after polymerization of said fibrous substrate impregnated with said liquid composition (LC1) according to the invention or said liquid composition (LC1) according to the invention mixed with a filler.

[0248] According to another additional aspect, the invention relates to a method for preparing a polymeric composition (PCI) or a composite material (CM1), said method comprising the following steps:

[0249] (i) supply of the liquid composition (LC1),

[0250] (ii) optionally adding a filler (Wire) to the liquid composition (LC1) or impregnating fibers or a fibrous substrate with the liquid composition (LC1),

[0251] (iii) polymerizing the liquid composition (LC1).

[0252] Another aspect of the present invention is a method for manufacturing composites or a composite material (CM1) by a process comprising the following steps:

[0253] i) impregnation of fibres or a fibrous substrate with the liquid composition (LC1), and

[0254] ii) polymerization of the liquid composition (LC1).

[0255] Impregnation can be achieved by resin transfer molding (RTM), pultrusion, infusion, spray layering or manual layering.

[0256] A first preferred embodiment of the manufacturing process for composites or composite material (CM1) includes impregnation by spray layering.

[0257] A second preferred embodiment of the manufacturing process for composites or composite material (CM1) includes resin transfer molding impregnation.

[0258] A third preferred embodiment of the manufacturing process for composites or composite material (CM1) includes impregnation by manual layering.

[0259] The process may include an additional heating step.

[0260] The process may also include the additional steps of providing fibers and providing the liquid composition (LC1).

[0261] Polymerizing the liquid composition (LC1) means that the (meth)acrylic monomer (M1) and the monomer (M2) of the liquid composition (LC1) are polymerized or copolymerized. This also means copolymerizing with the unsaturated polyester (UP1) or the vinyl ester resin (VE1), curing the precursor or prepolymer of the thermoset part, to establish a thermoset polymer.

[0262] In a first embodiment, the (meth)acrylic monomer (M1) and the monomer (M2) copolymerize with the unsaturated polyester (UP1).

[0263] In a second embodiment, the (meth)acrylic monomer (M1) and the monomer (M2) copolymerize with the vinyl ester resin (VE1).

[0264] In a third embodiment, at least part of the (meth)acrylic monomer (M1) and at least part of the monomer (M2) copolymerize with the unsaturated polyester (UP1) or the vinyl ester resin (VE1).

[0265] The polymerization of the liquid composition (LC1) that has impregnated the fibers or fibrous substrate takes place at a temperature between 0 °C and 120 °C, preferably between 10 °C and 110 °C. In a first preferred embodiment, the temperature is between 10 °C and 100 °C, in a second preferred embodiment the temperature is between 10 °C and 50 °C, and in a third preferred embodiment the temperature is between 50 °C and 110 °C.

[0266] If there is a polymerization activator or accelerator, the temperature may be lower compared to the case where no polymerization activator or accelerator is present in the liquid composition (LC1).

[0267] If the viscosity of the liquid composition (LC1) at a given temperature is slightly too high for the impregnation process, it is possible to heat the syrup to obtain a more liquid syrup for sufficient wetting and correct and complete impregnation of the fibrous substrate.

[0268] During the polymerization step of the liquid composition (LC1), the conversion of the (meth)acrylic monomer (M1) and the monomer (M2) of the liquid composition (LC1) which has impregnated the fibrous material is at least 80%, preferably 85%.

[0269] In a first preferred embodiment, the conversion of the (meth)acrylic monomer (Ml) and the monomer (M2) of the liquid composition (LC1) is 90%.

[0270] In a second preferred embodiment, the conversion of the (meth)acrylic monomer (Ml) and the monomer (M2) of the liquid composition (LC1) is 95%.

[0271] In a third preferred embodiment, the conversion of the (meth)acrylic monomer (Ml) and the monomer (M2) of the liquid composition (LC1) is 98%.

[0272] In a fourth preferred embodiment, the conversion of the (meth)acrylic monomer (Ml) and the monomer (M2) of the liquid composition (LC1) is 99%.

[0273] With regard to the use of mechanical parts made of composite material thus manufactured, many sectors can be cited, including in the housing, automotive, railway, sports, aeronautical, aerospace, photovoltaic or wind power sectors, and in marine or nautical applications, medical applications as well as sports applications, energy applications, transport applications, a storage application, construction and building applications, telecommunications applications.

[0274] The invention also relates to an object obtained with a liquid composition (LC1) or by the process or method.

[0275] The object is a mechanical part made of or comprising composite material.

[0276] By way of example, in the housing sector, these materials can be used for the manufacture of bathroom and / or kitchen equipment, such as countertops worktops, kitchen sinks, bathroom sinks, shower trays, bath panels or edging panels.

[0277] The mechanical part made of composite material or the article or object or molded part or mechanical part made of composite material comprising the polymer composition (PCI) prepared by polymerization of the liquid composition (LC1) is, in particular, a motor vehicle part, a boat part, a bus part, a train part, a sporting article, an airplane or helicopter part, a spacecraft or rocket part, a photovoltaic module part, a construction or building material, for example, composite reinforcing bars, dowels and stirrups for civil engineering and the construction of residential towers, a wind turbine part, for example a wind turbine blade beam spar flange, a piece of furniture, a construction or building part, a telephone or mobile phone part, a computer or television part, or a printer or photocopier part.

[0278] The mechanical part made of composite material is in particular a part of a marine vehicle or a part of a wind turbine blade.

[0279] In a first preferred embodiment the mechanical part made of composite material is a part of a nautical vehicle.

[0280] In a second preferred embodiment, the mechanical part made of composite material is in particular a part of a wind turbine blade.

[0281] As regards the recycling process, it relates to the recycling of a thermoset polymer comprising a composition (TPC) or of a composite comprising a thermoset polymer (TPCO) obtained by polymerization of the liquid composition (LC1).

[0282] The process optionally includes a cutting step. This is necessary if the apparatus used for the grinding step requires cutting into smaller pieces, or if the composition or composite or article to be recycled is too large for the grinding apparatus.

[0283] The grinding step reduces the composition or composite or article to be recycled using a grinding device. After the grinding step, a ground composition (GC1) is obtained.

[0284] The ground composition (GC1) comprises the polymer composition obtained after polymerization of the liquid composition (LC1) and other added components. If a composite comprising a thermoset polymer (TPCO) has been recycled, the ground composition (GC1) also includes portions of the fibrous substrate.

[0285] One of the advantages of the liquid composition (LC1) for preparing the composition comprising the thermoset polymer to be recycled (TPC) or the composite comprising the thermoset polymer (TPCO) obtained by polymerization of the liquid composition (LC1), is that the ground composition (GC1) obtained after the grinding step can be relatively coarse.

[0286] The ground composition (GC1) comprises ground particles of different shapes. There may be spherical particles, rod-like particles, needle-like particles, plate-like particles, flake particles, irregular angular particles.

[0287] By coarse, it is understood that there are ground particles in the ground composition (GC1) which in one dimension are larger than 0.5 mm, preferably 1 mm.

[0288] In one embodiment, there are ground particles in the ground composition (GC1) which in one dimension are larger than 2 mm.

[0289] In another embodiment, there are ground particles in the ground composition (GC1) which in one dimension are larger than 4 mm.

[0290] In yet another embodiment, there are ground particles in the ground composition (GC1) which in one dimension are larger than 6 mm.

[0291] In yet another embodiment, there are more than 50% of ground particles in the ground composition (GC1) which in one dimension are larger than 5 mm.

[0292] The ground material can be evaluated by optical microscopy in order to assess the respective shapes and sizes of the particles.

[0293] The ground composition (GC1) can be reused for example by making new composite materials by thermocompression. [Processes]

[0294] The weight-average molecular weight can be measured by size-exclusion chromatography (SEC). The chromatography column is calibrated with PMMA references having a molecular weight between 402 g / mol and 1,900,000 g / mol. The weight-average molecular weight is expressed in g / mol for the number and average molecular weights Mn and Mw, respectively. For the measurement, the concentration is 1 g / L.

[0295] The viscosity of the liquid composition comprising at least components a) and b) is measured using a Brookfield viscometer at 25 °C, according to ISO 2555:2018 “Plastics — Resins in liquid state or in emulsions or dispersions — Determination of apparent viscosity by the method of the single-cylinder type rotary viscometer”. Examples

[0296] A liquid composition is prepared by dissolving 30% by weight of PMMA (BS520), an MMA copolymer comprising ethyl acrylate as comonomer) as (PI) in 70 wt% of methyl methacrylate as (Ml), which is stabilized with HQME (hydroquinone monomethyl ether).

[0297] To this is added 100 parts of liquid (meth)acrylic composition (MCI), 0.4 phr by weight of N,N dimethylaniline and 1 phr of cobalt(II) 2-ethylhexanoate solution.

[0298] As composition (C2), an unsaturated polyester composition (UPC) is used: NORSYDYNE H 44382 TA from Polynt, having a viscosity of 440 mPa*s (Brookfield LV2 at 50 rpm), comprising about 45% by weight of styrene and 55% by weight of unsaturated polyester.

[0299] The liquid composition (LC1) is prepared by mixing the respective parts of the liquid (meth)acrylic composition (MCI) and composition (C2). The liquid composition (LC1) is finalized by adding 1.5 phr MEKP (Nouryon Butanox M50).

[0300] [Table 1] - compositions of the liquid composition (LC1) with respect to (MCI) and (C2) (MCI) [parts] (C2) [parts] Comparative Example 1 0 100 Example 1 100 100 Example 2 100 67

[0301] As a fibrous material, a 300 g / m2 glass fiber mat is used.

[0302] The impregnation of the fibrous material was carried out by manually layering.

[0303] Polymerization took place at approximately 20 °C for approximately 1 hour.

[0304] Several sheets reinforced with fibers were obtained with compositions according to Table 1.

[0305] To test the recycling of the composite, the sheets reinforced with respective polymerized fibers were pre-cut with a saw into pieces of approximate dimensions of 60 mm x 60 mm.

[0306] Next, for grinding, a ZM1 type mobile granulator was used, having a chamber dimension of 180 x 150 mm, using 6 rotor knives and 2 fixed knives.

[0307] Next, the desired grid with 6 mm, 12 mm, or 35 mm holes was installed. The composite parts were fed in and ground for a few minutes at 20 °C. The ground material was recovered. The 12 mm grid was primarily used.

[0308] The size of the ground material was mainly greater than 1 mm.

[0309] The ground material was introduced into a mold. The mold was closed, a slight pressure of approximately 5 bar was applied, and the mold was placed under a hot press at a temperature between 170 °C and 210 °C. Once the temperature was reached, a pressure of between 100 bar and 200 bar was applied for 5 minutes. The mold was then cooled to a temperature of approximately 50 °C, removed from the press, and opened. The molded part was demolded and visually assessed.

[0310] The evaluation is done by appearance; we evaluate whether the molded part obtained is homogeneous with the same surface appearance and whether there is no dry spot.

[0311] The symbol “—” means that the material is not at all homogeneous with the same surface appearance and that there are many dry spots.

[0312] The symbol “-” means that the material is not homogeneous with the same surface appearance and that there are some dry spots.

[0313] The symbol “+” means that the material is homogeneous with the same surface appearance and that there are no dry spots.

[0314] The symbol “++” means that the material is very homogeneous with the same surface appearance and that there are no dry spots.

[0315] [Table 2] - optical evaluation of respective molded parts obtained by recycling Optical evaluation Comparative example 1 — Example 1 + Example 2 ++

[0316] As can be seen in Table 2, the recycled molded products obtained after recycling composite sheets comprising the polymerized composition (LC1) of the invention exhibit a much better optical appearance and homogeneity.

Claims

Demands

1. Liquid composition (LC1) comprising: (a) 100 parts by weight of a liquid (meth)acrylic composition MCI comprising: (a) 10% by weight to 50% by weight of one or more (meth)acrylic polymers (PI), and (a2) 50% by weight to 90% by weight of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer, (b) 50 parts by weight to 150 parts by weight of a composition (C2) comprising either an unsaturated polyester (UPC) composition or a vinyl ester (VEC) composition comprising: (b1) 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and (b2) 20% by weight to 60% in weight of one or more monomers (M2), (c) optionally from 0.01 parts by weight to 7 parts by weight of a polymerization initiator (INI1), (d) optionally between 100 ppm and 20,000 ppm of an accelerator,

2. Liquid composition (LC1) according to claim 1, characterized in that it comprises, (c) from 0.01 parts by weight to 7 parts by weight of a polymerization initiator.

3. Liquid composition (LC1) according to claim 1 or 2, characterized in that it comprises: (d) between 100 ppm and 20,000 ppm of an accelerator.

4. Liquid composition (LC1) according to any one of claims 1 to 3, characterized in that it comprises: (e) a thixotropic agent.

5. Liquid composition (LC1) according to any one of claims 1 to 4, characterized in that composition (C2) is an unsaturated polyester (UPC) composition.

6. Liquid composition (LC1) according to any one of claims 1 to 4, characterized in that composition (C2) is a vinyl ester composition (VEC).

7. Liquid composition (LC1) according to any one of claims 1 to 6, characterized in that the liquid composition (LC1) comprises from 50 parts by weight to 100 parts by weight of composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

8. Liquid composition (LC1) according to any one of claims 1 to 6, characterized in that the liquid composition (LC1) comprises from 50 parts by weight to 80 parts by weight of composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

9. Liquid composition (LC1) according to any one of claims 1 to 6, characterized in that the liquid composition (LC1) comprises from 80 parts by weight to 150 parts by weight of composition (C2) comprising either an unsaturated polyester composition (UPC) or a vinyl ester composition (VEC) for 100 parts by weight of a liquid (meth)acrylic composition (MCI).

10. Liquid composition (LC1) according to any one of claims 1 to 9, characterized in that the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 4% by weight on the basis of a composition comprising the four components (a2) (meth)acrylic monomers (M1), (a1) (meth)acrylic polymers (PI), (b1) unsaturated polyesters (UP1) or a vinyl ester resin (VE1) and (b2) monomer (M2).

11. Liquid composition (LC1) according to any one of claims 1 to 9, characterized in that the amount of (meth)acrylic polymer (PI) in the liquid composition (LC1) is chosen to be at least 10% by weight on the basis of a composition comprising the four components (a2) (meth)acrylic monomers (M1), (a1) (meth)acrylic polymers (PI), (b1) unsaturated polyesters (UP1) or a vinyl ester resin (VE1) and (b2) monomer (M2).

12. A process for preparing the liquid composition (LC1) according to any one of claims 1 to 11, comprising the following steps: (i) supplying component (a), a liquid (meth)acrylic syrup comprising (a) from 1% by weight to 50% by weight of one or more (meth)acrylic polymers PI, and (a2) from 50% by weight to 99% by weight of one or more (meth)acrylic monomers Ml, each monomer Ml comprising only one (meth)acrylic function per monomer, (ii) addition for 100 parts of (a) of 50 to 150 parts by weight of component (b), optionally of component (c) of 0.01 parts by weight to 7 parts by weight of a polymerization initiator (INI1) and optionally of component (d) between 100 ppm and 20,000 ppm of an accelerator (iii) the mixing of components (a) with (b) or (a) with (d).

13. Use of the liquid composition (LC1) according to any one of claims 1 to 11 to prepare a polymeric composition (PCI).

14. Use of the liquid composition (LC1) according to any one of claims 1 to 11 to prepare a composite material (CM1).

15. Use of the liquid composition (LC1) according to any one of claims 1 to 11 to prepare a recyclable polymeric composition or a recyclable polymeric article or a recyclable composite composition or a recyclable polymeric composite all comprising a thermoset polymer.

16. Polymeric composition (PCI) prepared by polymerization of the liquid composition (LC1) according to any one of claims 1 to 11.

17. A process for preparing a polymeric composition (PCI) or a composite material (CM1), said process comprising the following steps: (i) supplying the liquid composition (LC1) according to any one of claims 1 to 11, (ii) optionally adding a filler (Fil) to the liquid composition (LC1) or impregnating the fibers or the fibrous substrate with the liquid composition (LC1), (iii) polymerizing the liquid composition (LC1).

18. A method for manufacturing composites, preferably composites comprising a thermoset polymer (TPCO), said method comprising the following steps: (i) impregnation of fibers or a fibrous substrate with a liquid composition (LC1) comprising: (a) 100 parts by weight of a liquid (meth)acrylic composition MCI comprising: (a1) 10% by weight to 50% by weight of one or more (meth)acrylic polymers (PI), and (a2) 50% by weight to 90% by weight of one or more (meth)acrylic monomers (Ml), each monomer (Ml) comprising only one (meth)acrylic function per monomer, (b) 50 parts by weight to 150 parts by weight of a composition (C2) comprising either an unsaturated polyester (UPC) composition or a vinyl ester (VEC) composition comprising: (b1) 40% by weight to 80% by weight of one or more unsaturated polyesters (UP1) or a vinyl ester resin (VE1), and (b2) 20 % by weight to 60% by weight of one or more monomers (M2), (c) possibly from 0.01 part by weight to 7 parts by weight of a polymerization initiator (INI1),(d) possibly between 100 ppm and 20,000 ppm of an accelerator ii) polymerization of the liquid composition (LC1).

19. The method according to claim 18, characterized in that the impregnation is carried out by resin transfer molding (RTM), pultrusion, infusion, spray layering or manual layering.

20. A method according to claim 18, characterized in that the impregnation is carried out by spraying layers or manually layering layers.

21. A process according to claim 18, characterized in that the polymerization of the liquid composition (LC1) which has impregnated the fibers or the fibrous substrate takes place at a temperature between 0 °C and 120 °C.

22. Thermosetting polymer comprising a composite (TPCO) comprising the liquid composition (LC1) polymerized according to any one of claims 1 to 11.

23. Article or object or molded part or mechanical part made of composite material comprising the polymer composition (PCI) according to claim 16 or comprising the composite material (CM1) prepared according to claim 17.

24. Article or object or molded object or mechanical part made of composite material according to claim 23 selected from a motor vehicle part, a boat part, a bus part, a train part, a sporting article, an airplane or helicopter part, a spacecraft or rocket part, a photovoltaic module part, a construction or building material, for example composite reinforcing bars, dowels and stirrups for civil engineering and the construction of residential towers, a wind turbine part, for example a wind turbine blade beam spar flange, a piece of furniture, a construction or building part, a telephone or mobile phone part, a computer or television part, or a printer or photocopier part.

25. A recycling process for a composition comprising a thermoset polymer (TPC) or a composite comprising a thermoset polymer (TPCO) obtained by polymerization of the liquid composition (LC1) according to any one of claims 1 to 3, said process comprising the following steps: - optionally a cutting step, - a grinding step of the composition comprising a thermoset polymer or of the composite comprising a thermoset polymer.

26. A process according to claim 25, characterized in that the grinding gives a ground composition (GC1) comprising ground particles in the ground composition (GC1) which, in one dimension, are larger than 0.5 mm, preferably 1 mm.

27. ​​A process according to claim 25, characterized in that the grinding gives a ground composition (GC1) comprising ground particles in the ground composition (GC1) which, in one dimension, are larger than 4 mm.